Polysiloxane-grafted copolymer topical binder composition with novel hydrophilic monomers and method of coating therewith

ABSTRACT

This invention relates to adhesives, surface modifying compositions, sealing compositions, and topical binder compositions comprising a copolymer having a vinyl polymeric backbone with grafted pendant siloxane polymeric moieties and especially to a method of topically applying such coating to animals.

This is a division of application Ser. No. 07/390,226 filed Aug. 7,1989, now U.S. Pat. No. 4,981,903.

BACKGROUND ART

Pressure sensitive adhesives and adhesive-coated sheet materials arewell-known in the art as having the ability to adhere toadhesive-receptive surfaces on mere contact. Such coated sheets in theform of labels and tapes, for example, can be adhered to varioussubstrates under very light "finger pressure" and can later be removedtherefrom by stripping the sheet from the surface to which it isattached. It is often desirable to reduce the initial affinity of a PSAfor a substrate while still maintaining sufficient ultimate adhesion(after pressure bonding). The prior art has attempted to achieve thisresult in various ways, mainly by use of different types of "physicalspacers" which have been mixed with or coated on the surface of the PSA.Such spacers act to hold the adhesive slightly away from the substratesurface until the desired placement has been achieved. For example, U.S.Pat. Nos. 3,314,838, 3,331,729, and 3,413,168, all assigned to thepresent assignee, disclose the use of hollow, spheroidal particles ormicroballoons composed of glass, urea- or phenol-formaldehyde resins,etc., to decrease initial adhesion and thereby provide positionability.The microballoons are described as being crushable or collapsible underapplied hand pressure, thereafter enabling the PSA to contact and adhereto the surface of the substrate. Fragments of the collapsed or crushedmicroballoons may, however, remain on the bonding surface of theadhesive rather than completely dispersed into the adhesive layer, andthis may, at least initially, adversely affect the adhesion strength.

Silicone has also been used as a spacing material to reduce the initialadhesion of PSA coatings and thereby produce positionable products. Forexample, U.S. Pat. No. 3,554,835 (Morgan Adhesives Company) discloses amethod of making and using a "slidable" PSA-coated laminate which reliesupon "dots" of silicone or other conventional release material asnon-adhesive spacers to enable initial positioning of the laminate on asubstrate. Similarly, United Kingdom Pat. No. 1,541,311 (UnitedMerchants and Manufacturers, Inc.) describes a PSA-coated laminate wherepositionability is provided by a uniform and discontinuous surfacecoating in the form of small beads or droplets of a non-tackypolysiloxane or polysiloxane-polyoxyalkylene block copolymer. Bothteachings require an additional manufacturing step or steps to apply thesilicone spacing material and to then effect solvent removal, drying, orcuring.

In U.S Pat. No. 4,151,319 (United Merchants and Manufacturers, Inc.) amethod for making a positionable PSA-coated laminate is disclosedwhereby polysiloxane or polysiloxane-polyoxyalkylene block copolymer isintimately mixed with the PSA itself rather than forming a coating onthe PSA surface. "Pre-mixing" of a siloxane polymer or copolymer in asuitable solvent prior to incorporation into the adhesive isrecommended. Again, the required mixing or dispersing and therecommended pre-mixing contribute additional process steps. The siloxaneadditives of this teaching are said to be in the form of small beads ordroplets dispersed throughout the adhesive mass, and thus some of thedroplets are positioned at the adhesive/release sheet interface of thelaminate (i.e., at the PSA surface) and function to allow initialpositioning on a substrate. The use of either block copolymers or highmolecular weight (above 25,000) polysiloxanes is suggested in UnitedKingdom Pat. No. 1,541,311 and U.S. Pat. No. 4,151,319 to minimize lossof adhesive mass, but the resultant laminates still may not offerpredictable levels of positionability even with minor losses.

U.S. Pat. No. 4,346,189 (Morgan Adhesives Company) describes the use ofpolysiloxane additives (of up to about 10,000 molecular weight) in adifferent type of application. The silicones are mixed with tackified,synthetic rubber-based PSA compositions to reduce edge ooze or flow uponcutting of sheets coated with such compositions. Either non-reactive orreactive polysiloxanes can be utilized and are said to appear to adsorbor graft onto other ingredients of the adhesives or take other unknownactions so as to produce the desired effect. It is stated, however, thatthe silicones can be added even at relatively high concentrations (6 to10% solids) without adversely affecting the adhesive characteristics ofthe material.

Graft copolymers some containing silicone, are being increasingly usedfor general modification of surface properties, as is described in aseries of papers by Y. Yamashita et al., [Polymer Bulletin 7, 289(1982); Polymer Bulletin 10, 368 (1983); Makromol. Chem. 185, 9 (1984);Macromolecules 18, 580 (1985)]. Such use is also reflected in somerecent Japanese art, such as Japanese Patent Application No. 57-179246,published Nov. 4, 1982, which concerns the use of graft copolymers asadditives to impart long-lasting hydrophobicity (or hydrophilicity) tosurfaces. In Japanese Patent Applications Nos. 58-167606, published Oct.3, 1983, and 58-154766, published Sept. 14, 1983, a method ofpreparation of silicone graft copolymers and the use of these copolymersin coating compositions such as paint films are described. Here, thecopolymers are said to provide long-lasting water- and oil-repellency,stain resistance, and reduced frictional properties. Japanese PatentApplication No. 59-78236, published May 7, 1984, discloses a method ofpreparing monofunctional polymeric silicone monomers, i.e.,macromonomers, for use in the preparation of graft copolymers assurface-treatment agents. The use of such silicone macromonomer-graftedcopolymers in coating compositions, again to impart lasting water- andoil-repellency, stain resistance, and low friction characteristics, isdescribed in Japanese Patent Application No. 59-126478, published July21, 1984. U.S. Pat. No. 4,728,571 discloses the use of tack-freepolysiloxane-grafted copolymers (and blends thereof with other polymericmaterials) as release coating compositions for PSA-coated sheetmaterials and the back side of PSA-coated tapes.

U.S. Pat. No. 4,693,935 teaches polysiloxane-grafted copolymer pressuresensitive adhesive compositions and sheet materials coated therewith.The invention is directed specifically towards pressure sensitiveadhesives and articles coated therewith.

SUMMARY OF THE INVENTION

The present invention provides a composition which is pressure-sensitiveor non-pressure-sensitive adhesive at room temperature (20.0° C.) andwhich comprises a copolymer which has pendant polysiloxane grafts.Similar polymers, but with lower Tg's (glass transition temperatures)and different preferred monomers contain the pendant polysiloxane graftsto cause the exposed surface of a layer of the adhesive composition toinitially have a lower degree of adhesiveness to provide in effect atemporary "low adhesion frontsize". Upon application, however, thependant polysiloxane grafts in the prior art (U.S. Pat. No. 4,693,935)appear to migrate into the body of the layer and the adhering surfacebuilds adhesiveness to form a strong adhesive bond. Thus a temporarychemical surface modification of the pressure-sensitive adhesivecomposition is effected such that positionability of an article bearingthe coating of pressure-sensitive adhesive is possible without many ofthe aforementioned difficulties of the prior art. The present invention,however, can utilize copolymers wherein a slightly different combinationand proportion of monomers is selected so that no significantpressure-sensitive characteristics are provided, but the polymers arefound to have good topical application binding characteristics, as forfinishings to glass, ceramics, metal, and wood as well as for theapplication of cosmetics and medicaments. The polymers may also be usedas sealing compositions for porous materials such as paper and wood.

Chemical incorporation of the polysiloxane into the copolymers of thepresent invention prevents siloxane loss. Predictable degrees ofsolubility and bondability are thus reliably achieved for a variety ofcompositions.

The compositions of this invention comprise a copolymer, the backbone ofwhich has grafted to it monovalent siloxane polymeric moieties having anumber average molecular weight above about 500 (preferably from about500 to about 50,000, most preferably from about 5,000 out 25,000). Ifthe copolymer has components with Tg's (in their polymerized state) over20.0° C., the composition can be non-tacky at 20.0° C. and 0.5 Kg/cm².

More specifically, the composition of the invention comprises thefollowing elements:

a) a copolymer which comprises repeating A, C, and, B monomers(preferably non-pressure-sensitive compositions wherein the compositionhas a glass transition temperature of at least 20.0° C., preferably30.0° C., and most preferably 40.0° C.) and wherein:

A is at least one free radically polymerizable acrylate or methacrylate(hereinafter referred to as "(meth)acrylate") monomer present as 0.1 to99.9% and for some compositions present as at least 40% of the totalweight of the monomers up to 99%;

B is at least one reinforcing monomer copolymerizable with A, the amountby weight of B monomer being present as 0.1 to 99.9% by weight of themonomers and in some cases as at least about 3.0 to a maximum of 30% ofthe total weight of all monomers; and

C is a monomer, present as 0.01 to 50% by weight of all monomerspreferably 3 to 30%, m the general formula X(Y)_(n) Si(R)_(3-m) Z_(m)wherein

X is a vinyl group copolymerizable with the A and B monomers;

Y is a divalent linking group (e.g., alkylene, arylene, alkarylene, andaralkylene of 1 to 30 carbon atoms) and incorporating e.g. ester, amide,urethane, urea groups.

n is zero or 1;

m is an integer of from 1 to 3;

R is hydrogen, lower alkyl (e.g., 1 to 4 carbon atoms, methyl, ethyl, orpropyl), aryl (e.g., 6 to 20 carbon atoms, phenyl or substitutedphenyl), or alkoxy (preferably lower alkoxy of 1 to 4 carbon atoms);

Z is a monovalent siloxane polymeric moiety having a number averagemolecular weight above about 500 and is essentially unreactive undercopolymerization conditions;

wherein the monomers are copolymerized to form the polymeric backbonewith the C monomer grafted thereto;

b) optionally at least 0.1 up to about 500 parts of a surfaceconditioner, sealing component, medicament, or skin or hair softening orconditioning ingredient per 10 parts copolymer; and

c. up to about 500 parts of a compatible solvent or plasticizer per 10parts copolymer.

This invention also provides a process for applying the coatingcomposition to various surfaces such as wood, paper, metal, glass,polymers and animal bodies comprising the application of the compositioncontaining medicaments, conditioning, sealing or softening ingredientsto at least a portion of one major surface of a surface or body. Theinvention also provides specific products comprising the compositionwith particular classes of additives.

DETAILED DESCRIPTION

The copolymers of the invention have a well-defined structure, having a(meth)acrylic polymeric backbone which has been chemically modified bythe addition of a small weight percentage of polysiloxane grafts. Whensuch copolymers are coated on an exposed area of an animal body or onanimal hair, non-tacky coatings or localized applications can beaesthetically and comfortably made on those bodies. Once applied to asurface, the composition can maintain the presence of active ingredientsapplied in the composition.

The surface characteristics of the copolymeric adhesive composition canbe chemically tailored through variation of both the molecular weight ofthe grafted siloxane polymeric moiety and the total siloxane content(weight percentage) of the copolymer, with higher siloxane contentand/or molecular weight providing lower initial adhesion The chemicalnature and the molecular weight of the methacrylic polymeric backbone ofthe copolymer can also be chosen such that the level of adhesion to thesubstrate can be matched to the requirements of a particularapplication. Since their siloxane content is relatively low, thecopolymers of this invention are readily compatible with siloxane-freepolymers, for example polymers of composition similar to that of thevinyl or methacrylic backbone.

The preferred method of preparation of the compositions of the inventionprovides graft copolymer of high purity which can be coated directlyfrom the polymerization solvent, if necessary or desired. The resultantcoatings do not require curing or crosslinking. However, if enhancementof either shear strength or resistance to solvents or photochemical oroxidative forces is desired, cross)inking may be effected by standardmethods well-known in the art, such as radiation curing (electron beamor ultraviolet light) or chemical crosslinking.

The siloxane polymeric moieties can be grafted by polymerizing monomeronto reactive sites located on the backbone, by attaching preformedpolymeric moieties to sites on the backbone, or, preferably, bycopolymerizing the methacrylic monomer(s), A, and, polar monomer(s), B,with preformed polymeric siloxane monomer, C. Since the polymericsiloxane surface modifier is chemically bound, it is possible tochemically tailor the compositions of this invention such that aspecific degree of cohesiveness and solubility are provided and can bereproduced with consistency.

As previously mentioned, the composition of this invention comprises a(meth)acrylate copolymer in which monovalent siloxane polymeric moietieshaving a number average molecular weight above about 500 are grafted tothe copolymer backbone. The copolymer preferably consists essentially ofcopolymerized repeating units from A, B, and C monomers.

The A monomer or monomers (there may be more than one) are chosen suchthat a non-tacky material is obtained upon polymerization of A (or A andB). Representative examples of A monomers are the lower to intermediatemethacrylic acid esters of alcohols such as methanol, ethanol,1-propanol, 2-propanol, 1-butanol, 1,1-dimethyl ethanol,2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol,2-methyl-1-butanol, 3-methyl-1-butanol, 2-hexanol, 2-methyl-1-pentanol,3-methyl-1-pentanol, cyclohexanol, 2-ethyl-1-butanol, 3-heptanol, benzylalcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, and1-dodecanol, and the like, the alcohols having from 1 to 12 carbonatoms, preferably 1 to 8 carbon atoms, with the average number of carbonatoms being about 4-12. Some small amount of copolymerizable styrene,vinyl esters, vinyl chloride, vinylidene chloride, acryloyl monomers andthe like may be used. Such monomers are known in the art, and many arecommercially available. Preferred polymerized A monomer backbonecompositions include poly(isooctyl methacrylate), poly(isononylmethacrylate), poly(2-ethylhexyl methacrylate),polyisopentylmethacrylate, poly(n-butyl methacrylate), poly(isobutylmethacrylate), poly(methylmethacrylate), and copolymers thereof withother A monomer or monomers. Some amount of acrylate may also bepresent, but only in such amounts that these compositions are notpressure sensitive.

The B monomers according to the practice of the present invention arehighly polar acrylic and methacrylic monomers. A highly polar monomer asdefined in the practice of the present invention are acrylic ormethacrylic monomers having at least one highly polarizing group such ashydroxy(OH), amino (primary, secondary, and tertiary), and ionic groups(e.g., quaternary ammonium, carboxylate salt, sulfonic acid salt, etc.)

The hydrophilic `B` monomers may be mono- or multifunctional hydroxygroup containing molecules represented by the general formula

    CH.sub.2 ═CR.sup.2 --CO--L--R.sup.3 --(OH).sub.4

where R² =H, methyl, ethyl, cyano or carboxymethyl, L=O, NH, d=1-3 andR³ is a hydrocarbyl radical of valence d+1 containing from 1-2 carbonatoms. The preferred monomers in this class are hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl(meth)acrylate, glycerol mono(meth)acrylate, tris(hydroxymethyl)ethanemonoacrylate, pentaerythritol mono(meth)acrylate, N-hydroxymethyl(meth)acrylamide, hydroxyethyl (meth)acrylamide and hydroxypropyl(meth)acrylamide.

The hydrophilic monomer `B` may belong to the class II of mono- ormultifunctional amino group containing molecules of the general formula:

    CH.sub.2 ═R.sup.2 --CO--L--R.sup.3 --(NR.sup.4 R.sup.5).sub.d

where R², L, R³, and d are as defined above and R⁴ and R⁵ are H or alkylgroups of 1-12 carbon atoms or together they constitute a carbocyclic orheterocyclic group. Preferred monomers of this class are aminoethyl(meth)acrylate, aminopropyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate,N,N-dimethylaminopropyl (meth)acrylamide, N-isopropylaminopropyl(meth)acrylamide and 4-methyl-1-acryloyl-piperazine.

The hydrophilic `B` monomers may also be alkoxy substituted(meth)acrylates or (meth)acrylamides such as methoxyethyl(meth)acrylate, 2(2-ethoxyethoxy)ethyl (meth)acrylate, polyethyleneglycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

Particularly useful are `B` monomers that have Substituted orunsubstituted ammonium groups of the general formula: ##STR1## where R²,R³, R⁴, R⁵, L and d are as defined above, and where R⁶ is H or alkyl of1-12 carbon atoms and Q⁻ is an organic or inorganic anion. Preferredexamples of such monomers are 2-N,N,N-trimethylammonium ethyl(meth)acrylate, 2-N,N,N-triethylammonium ethyl (meth)acrylate,3-N,N,N-trimethylammonium propyl (meth)acrylate,N(2-N',N',N'-trimethylammonium) ethyl (meth)acrylamide, N-(dimethylhydroxyethyl ammonium) propyl (meth)acrylamide etc. where the counterionmay be chloride, bromide, acetate, propionate, laurate, palmitate,stearate etc. The monomer can also be N,N-dimethyl diallyl ammonium saltof an organic or inorganic counterion.

Ammonium group containing polymers can also be prepared by using as the`B` monomer, any of the amino group containing monomer described above,and acidifying the resultant polymers with organic or inorganic acid toa pH where the pendant amino groups are substantially protonated.Totally substituted ammonium group containing polymers may be preparedby alkylating the above described amino polymers with alkylating groups,the method being commonly known in the art as the Menschutkin reaction.

The hydrophilic `B` monomers of the invention can also be sulfonic acidgroup containing monomers e.g. vinyl sulfonic acid, styrene sulfonicacid, 2-acrylamido-2-methyl propane sulfonic acid, allyloxybenzenesulfonic acid etc. These monomers may be used in the protonated acidform as monomers and the corresponding polymers obtained may beneutralized with an organic or inorganic base to give the salt form ofthe polymers.

The hydrophilic `B` monomers can be other alkenyl heterocycles such asvinyl imidazoles, vinyl benzimidazoles, vinyl azlactones, vinyl furansetc. These heterocyclic comonomers provide sites for hydrogen bondingwith polar substrates and improve adhesion of the resultant polymers tosuch substrates.

Incorporation of B monomer to the extent of about 2% to about 25% byweight is most preferred and provides compositions of high cohesive orinternal strength, good adhesion to polar surfaces and which alsoretains good physical properties.

The preferred C monomer may be further defined as having an X groupwhich has the general formula ##STR2## wherein R⁷ is a hydrogen atom ora COOH group and R⁸ is a hydrogen atom, a methyl group, or a CH₂ COOHgroup.

The Z group of the C monomer has the general formula ##STR3## where R⁹and R¹¹ are independently lower alkyl, aryl, or fluoroalkyl, where loweralkyl and fluoroalkyl both refer to alkyl groups having from one tothree carbon atoms and where aryl refers to phenyl or substituted phenyl(of up to 20 carbon atoms). R¹⁰ may be alkyl (of 1 to 20 carbon atoms),alkoxy (of 1 to 20 carbon atoms), alkylamino (of 1 to 20 carbon atoms),aryl (of up to 20 carbon atoms), hydroxyl, or fluoroalkyl (of 1 to 20carbon atoms), and e is an integer from about 5 to about 700.Preferably, the C monomer has a general formula selected from the groupconsisting of the following, where m is 1, 2, or 3, g is zero or 1, R"may be alkyl (of 1 to 10 carbon atoms) or hydrogen, f is an integer from2 to 6, h is an integer from zero to 2, and X, R, and Z are as definedabove: ##STR4##

The topical composition of this invention is provided by copolymerizingthe A, B and C, and, preferably, B monomers followed, when necessary ordesirable, by blending with a compatible cosmetic or medicinally activeingredient in order to optimize the ultimate utile properties of thecomposition.

When the above described composition is coated on skin or hair in properproportions in a composition, no tackiness is observed when thecomposition is dry. Copolymers containing C monomer having a molecularweight less than about 500 are not very effective in providingsubstantivity, or persistant retention on the skin. Copolymerscontaining C monomer having a molecular weight greater than 50,000effectively provide substantivity, but, at such high molecular weights,possible incompatibility of the C monomer with the remaining monomerduring the copolymerization process may result in reduced incorporationof C. Molecular weight of C monomer ranging from about 500 to about50,000 is therefore preferred. A molecular weight range from about 5,000to about 25,000 is most preferred.

The C monomer is preferably incorporated in the copolymer in the amountof about 0.01 to about 50% of the total monomer weight to obtain thedesired properties. The amount of C monomer included may vary dependingupon the particular application, but incorporation of such percentagesof C monomer having a molecular weight in the above-specified range hasbeen found to proceed smoothly and to result in material which provideseffective substantivity for a variety of applications while still beingcost effective.

The C monomers of this invention are terminally functional polymershaving a single functional group (the vinyl, ethylenically unsaturated,acryloyl, or methacryloyl group) and are sometimes termed macromonomersor "macromers". Such monomers are known and may be prepared by themethod disclosed by Milkovich et. al., as described in U.S. Pat. Nos.3,786,116 and 3,842,059. The preparation of polydimethylsiloxanemacromonomer and subsequent copolymerization with vinyl monomer havebeen described in several papers by Y. Yamashita et al., [Polymer J. 14,913 (1982); ACS Polymer Preprints 25 (1), 245 (1984); Makromol. Chem.185, 9 (1984)]. This method of macromonomer preparation involves theanionic polymerization of hexamethylcyclotrisiloxane monomer (D₃) toform living polymer of controlled molecular weight, and termination isachieved via chlorosilane compounds containing a polymerizable vinylgroup. Free radical copolymerization of the monofunctional siloxanemacromonomer with vinyl monomer or monomers provides siloxane-graftedcopolymer of well-defined structure, i.e., controlled length and numberof grafted siloxane branches.

Suitable monomers for use in the above-mentioned anionic polymerizationare, in general, diorganocyclosiloxanes of the formula ##STR5## where R⁹and R¹¹ are as previously defined and where e is an integer of 3 to 7.Preferred are the cyclic siloxanes where e is 3 or 4 and R⁹ and R¹¹ areboth methyl, these cyclic siloxanes being hereafter designated D₃ andD₄, respectively. D₃, which is a strained ring structure, is especiallypreferred.

Initiators of the anionic polymerization are chosen such thatmonofunctional living polymer is produced. Suitable initiators includealkali metal hydrocarbons such as alkyl or aryl lithium, sodium, orpotassium compounds containing up to 20 carbon atoms in the alkyl oraryl radical or more, preferably up to 8 carbon atoms. Examples of suchcompounds are ethylsodium, propylsodium, phenylsodium, butylpotassium,octylpotassium, methyllithium, ethyllithium, n-butyllithium,sec-butyllithium, tert-butyllithium, phenyllithium, and2-ethylhexyllithium. Lithium compounds are preferred as initiators. Alsosuitable as initiators are alkali metal alkoxides, hydroxides, andamides, as well as triorganosilanolates of the formula ##STR6## where Mis alkali metal, tetraalkylammonium, or tetraalkylphosphonium cation andwhere R⁹, R¹⁰, and R¹¹ are as previously defined. The preferredtriorganosilanolate initiator is lithium trimethylsilanclate (LTMS). Ingeneral, the preferred use of both strained cyclic monomer and lithiuminitiator reduces the likelihood of redistribution reactions and therebyprovides siloxane macromonomer of narrow molecular weight distributionwhich is reasonably free of unwanted cyclic oligomers.

Molecular weight is determined by the initiator/cyclic monomer ratio,and thus the amount of initiator may vary from about 0.004 to about 0.4mole of organometallic initiator per mole of monomer. Preferably, theamount will be from about 0.008 to about 0.04 mole of initiator per moleof monomer.

For the initiation of the anionic polymerization, an inert, preferablypolar organic solvent can be utilized. Anionic polymerizationpropagation with lithium counterion requires either a strong polarsolvent such as tetrahydrofuran, dimethyl sulfoxide, orhexamethylphosphorous triamide, or a mixture of such polar solvent withnonpolar aliphatic, cycloaliphatic, or aromatic hydrocarbon solvent suchas hexane, heptane, octane, cyclohexane, or toluene. The polar solventserves to "activate" the silanolate ion, making propagation possible.

Generally, the polymerization can be carried out at a temperatureranging from about -50.0° C. to about 100° C., preferably from about-20.0° C. to about 30.0° C. Anhydrous conditions and an inert atmospheresuch as nitrogen, helium, or argon are required.

Termination of the anionic polymerization is, in general, achieved viadirect reaction of the living polymeric anion with halogen-containingtermination agents, i.e., functionalized chlorosilanes, to producevinyl-terminated polymeric monomers. Such terminating agents may berepresented by the general formula X(Y)_(n) Si(R)_(3-m) Cl_(m), where mis 1, 2, or 3 and where X, Y, n, and R have been previously defined. Apreferred terminating agent is methacryloxypropyldimethylchlorosilane.The termination reaction is carried out by adding a slight molar excessof the terminating agent (relative to the amount of initiator) to theliving polymer at the polymerization temperature. According to theaforementioned papers by Y. Yamashita et al., the reaction mixture maybe ultrasonically irradiated after addition of the terminating agent inorder to enhance functionality of the macromonomer. Purification of themacromonomer can be effected by addition of methanol.

The copolymerization of the A monomer, B monomer and C monomer iscarried out by conventional free radical polymerization such asdescribed by Ulrich, U.S. Pat. No. Re. 24,906. The monomers aredissolved in an inert organic solvent and polymerized utilizing asuitable free radical initiator which can be either thermally orphotochemically activated. Suitable thermally activated initiatorsinclude azo compounds such as 2,2'-azobis (isobutyronitrile),hydroperoxides such as tert-butyl hydroperoxide, and peroxides such asbenzoyl peroxide or cyclohexanone peroxide, and suitable photochemicallyactivated initiators include benzophenone, benzoin ethyl ether, and2,2-dimethoxy-2-phenyl acetophenone. The amount of initiator used isgenerally about 0.01 to about 5% by weight of the total polymerizablecomposition.

The organic solvent used in the free radical copolymerization can be anyorganic liquid which is inert to the reactants and product and whichwill not otherwise adversely affect the reaction. Suitable solventsinclude ethyl acetate and mixtures such as ethyl acetate with toluene orheptane with toluene and isopropyl alcohol. Other solvent systems mayalso be used. The amount of solvent is generally about 30-80% by weightof the total weight of reactants and solvent. In addition to solutionpolymerization, the copolymerization can be carried out by otherwell-known techniques such as suspension, emulsion, and bulkpolymerization.

As described above, the preferred grafting technique involvescopolymerization of (meth)acrylic monomer, A, reinforcing monomer, B,and chemically tailored macromonomer, C, of controlled molecular weight.Other grafting techniques can be employed, each providing a degree ofpredictability of the properties of the end product. One alternativetechnique involves preforming the methacrylic polymeric backbone, thencopolymerizing this preformed backbone with cyclic siloxane monomer.Another approach is to graft preformed monofunctional siloxane polymerto a preformed methacrylic polymeric backbone. These and other polymergrafting techniques are described by Noshay and McGrath in BlockCopolymers, Academic Press, New York (1977), pages 13-16 and in greaterdetail by Battaerd and Tregear in Graft Copolymers, J. Wiley and Sons,New York (1967).

The copolymeric topically applied compositions of this invention insolution or dispersion are easily coated upon suitable body areas butnot areas of the primary integumentary system, e.g., hair on the scalp.The compositions maybe used on areas with vestigial hair (such as theface and arms and legs) but are not intended in the practice of theinvention as primary treatments for hair. They are also not preferredfor treatments in the lining of the eye or nasal passage. Non-mucosalareas of the body of non-aqueous dwelling mammals are particularlypreferred and fur treatments for non-human animals are also preferred(dogs, cats, rabbits, etc.). The compositions with other appropriateadditives may be used as adhesives, conditioning treatments for organicor inorganic surfaces, and sealants for wood or paper.

The compositions of this invention may be coated by any of a variety ofconventional coating techniques such as wiping, spraying, handspreading, swab application, and the like.

The topical application of medicaments to the skin has traditionallybeen done with the application of self-sustaining or self-supportingcohesive articles such as films, tapes, or plasters as a proposedimprovement over direct applications of powders, ointments, creams,lotions or the like. It has been felt that these more substantial mediaprovided a longer lasting and more controllable application of medicineto the skin or hair of a mammal. These medical applications suffer fromdistinct problems of their own, however. All of the films and tapes tendto be uncomfortable as they cannot completely conform with stretching,bending, or wrinkling which the exterior surfaces of bodies undergoduring movement. The films, tapes and plasters are not cosmeticallyacceptable, especially if applied to the face and hands, which areexposed to view. Films and tapes are easily and accidentally removed, inpart or in whole, from the skin by inadvertent contact or perspirationoccurring under the film or tape. This directly reduces the medicalefficiency of the application. Films and tapes can trap moisture againstthe surface which can be medically disadvantageous and can block oxygenpenetration to the surface. The application of thin polymer films willnot solve these problems because the films can be readily broken anddelivery of the medicine can be interrupted.

It has been found in the present invention that by selecting onlyappropriate proportions of medicaments and the non-pressure-sensitiveadhesive polymeric binders in solutions, emulsions, or dispersions thatan extremely effective topical application of medicaments, and skintreatments, and fur of hair treatments for animals other than humans maybe performed. The proportions are selected, contrary to conventionalwisdom, so that a non-cohesive, non-tacky coating of the binder andmedicament is formed on the skin particularly in non-mucosal areas.

Medicaments according to the practice of the present invention are thosecompounds or materials which have a direct medicinal or neurologicaleffect (excluding alcohols). Materials which have a beneficial activityagainst the growth, propogation or survival of bacteria, fungi, orviruses or which are antihistamines, antitoxins, anaesthetics,analgesics, antipruritics, vitamins, and antiinflammatants are includedin the term medicaments. These materials are well known in the medicalart and no exhaustive list is thought to be necessary. Exemplarycompounds include hydrocortisone acetate, undecylenic acid, tolnaftate,methyl salicylate, lidocaine, oxytetracycline.HCl, retinoic acid,Minoxidil®, etc. These medicaments may provide the medicinal activity atthe site of application or upon absorption through the skin.

These medicaments are combined in the critical proportions of thisinvention with the oil compatible non-pressure sensitive adhesives.Pressure-sensitive adhesives are art recognized as a standard class ofmaterials. These are adhesives which in dry (substantially solvent freeexcept for residual solvent) form are aggressively and permanently tackyat room temperature (e.g., 15.0° to 25.0° C.) and firmly adhere to avariety of dissimilar surfaces upon mere contact without the need formore than manual pressure. They require no activation by water, solventor heat in order to exert a strong adhesive holding force towards suchmaterials as paper, cellophane, glass, wood and metals. They have asufficiently cohesive holding and elastic nature so that, despite theiraggressive tackiness, they can be handled with the fingers and removedfrom smooth surfaces without leaving a substantial residue (cf. TestMethod for Pressure-Sensitive Tapes, 6th Ed., Pressure Sensitive TapeCouncil, 1953). Pressure-sensitive adhesives and tapes are well known,and the wide range and balance of properties desired in such adhesiveshas been well analyzed (cf. U.S. Pat. No. 4,374,883; and"Pressure-Sensitive Adhesives" in Treatise on Adhesion and AdhesivesVol. 2, "Materials", R. I. Patrick, Ed., Marcel Dekker, Inc., N.Y.,1969). The various materials and compositions useful aspressure-sensitive adhesives are available commercially and arethoroughly discussed in the literature (e.g., Houwink and Salomon,Adhesion and Adhesives, Elsevier Publ. Co., Amsterdam, Netherlands,1967; Handbook of Pressure-Sensitive Adhesive Technology, Donates Satas,Ed., VanNostrand Reinhold Co., N.Y., 1982).

Pressure-sensitive adhesives are generally chemically composed ofrubber-resin materials, acrylic resins, polyurethane resins, siliconeresins, and the like. Among the various patent literature describingcompositions and improvements in pressure-sensitive adhesiveformulations are U.S. Pat. No. Re. 24,906; U.S. Pat. Nos. 2,652,351;3,740,366; 3,299,010; 3,770,708; 3,701,758; 3,922,464; 3,931,087;4,012,560; 4,077,926; 4,387,172; 4,418,120; 4,629,663; and the like.These classes of rubber resin, acrylic, silicone and polyurethanepressure-sensitive adhesives as well as any other pressure-sensitiveadhesives are not generally useful in the present invention. Onlynon-pressure sensitive adhesives are used in the detailed proportions ofthe present invention, and non-tacky applications of medicaments areprovided. The polymers useful in the present invention are oilcompatible (dispersible, swellable, or soluble in organic oils andnon-polar solvents) and generally are clearly hydrophobic in theirproperties.

The molecular weight of the polymers used in the compositions may varyover a broad range. The molecular weight must be suitably large toprovide the requisite binding effect. The upper limit is determined onlyby formulation requirements. As the molecular weight increases, thepolymers tend to become too viscous to formulate easily intocosmetically-appealing compositions. Generally, polymers having aBrookfield viscosity between 50 and 100,000 cps and preferably between500 and 15,000 cps, when measured at 16.6 percent non-volatiles, will beuseful in the compositions of the invention.

The compositions of the invention are of three basic types, i.e., oils,water-in-oil and oil-in-water emulsions. The oil formulations areprepared by mixing the oil base, polymer and active ingredient (e.g.,medicament) together and warming the mixture with slow agitation toabout 140° F. The water phase ingredients, if part of an emulsionformulation, are combined and heated to 180° F. This phase is slowlyadded to the oil phase ingredients, also at 180° F., and the combinationallowed to cool with agitation. The formulations generally contain about0.5 to 10 percent by weight of the acrylate polymer, with the preferredrange being from about 0.5 to 5.0 percent by weight. At levels below0.25 percent, the polymer is less effective in holding a significantamount of the active ingredient (e.g., medicament) on the skin when theskin is exposed to water. At levels above 10 percent, the formulationgenerally becomes sticky and develops an unpleasant feeling.

The cosmetic oil base, if any, of the compositions may be solid orliquid, but the entire formulation should be somewhat fluid at skintemperatures for ease of application. Fragrances, fillers, dyes,colorants, preservatives, antioxidants and other such material may beincluded in minor amounts in the compositions without affecting thesubstantivity of the composition.

When applied to human skin, these products form films of the medicamenton the skin surface. The polymer dispersed therein holds the medicamentor chemical treatment onto the skin so that a significantly greaterpharmacological or cosmetic benefit is provided than the compositionswithout the polymer.

As indicated above, the composition to be applied to topical areas ofmammals (generally non-water dwelling mammals) comprises 0.25-10% bytotal weight of polymer, preferably 0.5 to 5 percent by weight, and mostpreferably 0.5 to 2% by weight of polymer per total weight ofcomposition. The active ingredient or medicament may be present in abroader weight range of 0.1 to 50% by total weight of the composition,preferably 0.25 to 20% by weight, more preferably 0.5 to 10% and mostpreferably 1 to 3% by weight. The ratio of the polymer to medicament(wt. polymer/wt. medicament) should also be in the range of 1/5 to 1/50to achieve the benefits of the present invention.

These and other aspects of the invention will be shown in the followingnon-limiting examples.

EXAMPLES 1-3

Polymerizations of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N,N-dimethylaminoethyl methacrylate (DEMAEMA)and iso-butyl methacrylate (IBM).

To a mixture of 20 parts of PDMS (MW=20,000), 10-30 parts of DMAEMA and50-70 parts of IBM in 200-300 part of toluene or ethyl acetate was added0.05-0.5 parts of azobis(isobutyronitrile) (AIBN). This solution waspurged with nitrogen atmosphere. The bottle was heated in an AtlasLaunder-O-Meter® at 60° C. for 36-48 hours and the polymer was recoveredby evaporation of solvent under reduced pressure.

    ______________________________________                                        Example  PDMS          DMAEMA    IBM                                          ______________________________________                                        1        20            10        70                                           2        20            20        60                                           3        20            30        50                                           ______________________________________                                    

EXAMPLES 4-5

Polymerizations of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N,N-dimethylaminoethyl methacrylate (DMAEMA)and n-butyl methacrylate (NBM).

To a mixture of 20 parts of PDMS (MW=20,000, 5-20 parts of DMAEMA and60-75 parts of NBM in 200-300 parts of toluene or ethyl acetate wasadded 0.05-0.5 parts of azobisisobutyronitrile (AIBN). This solution waspurged with nitrogen and sealed in a bottle under a nitrogen atmosphere.The bottle was heated in a Launder-O-Meter® at 60° C. for 36-48 hoursand the polymer was recovered by evaporation of solvent under reducedpressure.

    ______________________________________                                        Example   PDMS        DMAEMA    NBM                                           ______________________________________                                        4         20          20        60                                            5         20           5        75                                            ______________________________________                                    

EXAMPLES 6-8

Polymerizations of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with N,N-dimethylaminoethyl methacrylate (DMAEMA),2-ethylhexyl methacrylate (EHM) and iso-butyl methacrylate (IBM).

To a mixture of 20 parts of PDMS (MW--20,000), 15-25 parts of DMAEMA, 10parts of EHM and 45-55 parts of IBM in 200-300 parts of toluene or ethylacetate was added 0.05-0.5 parts of azobis(isobutyronitrile) (AIBN).This solution was purged with nitrogen and sealed in a bottle under anitrogen atmosphere. The bottle was heated in a Launder-O-Meter® at 60°C. for 36-48 hours and the polymer was recovered by evaporation ofsolvent under reduced pressure.

    ______________________________________                                        Example   PDMS    DMAEMA       EHM   IBM                                      ______________________________________                                        6         20      15           10    55                                       7         20      20           10    50                                       8         20      25           10    45                                       ______________________________________                                    

EXAMPLE 9

Polymerizations of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with 2-hydroxyethyl methacrylate (HEMA) and isobutylmethacrylate (IBM).

To a mixture of 20 parts of PDMS (MW=20,000), 20 parts of HEMA and 60parts of IBM in 200 parts of ethyl acetate was added 0.5 parts ofbenzoyl peroxide and 10 parts of isopropanol. This solution was purgedwith nitrogen and sealed in a bottle under a nitrogen atmosphere. Thebottle was heated in a Launder-O-Meter® at 60° C. for 48 hours and thepolymer was recovered by evaporation of solvent under reduced pressure.

EXAMPLE 10

Polymerizations of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with ethyl cyanoacrylate (ECA) and isobutylmethacrylate (IBM).

To a mixture of 20 parts of PDMS (MW=20,000) and 60 parts of IBM wasadded 20 parts of ECA. This mixture immediately began to polymerize andon allowing to stand at room temperature for 4-6 hours had completelysolidified to a polymeric mass. The polymer was recovered by evaporationof all volatiles under reduced pressure.

EXAMPLES 11-12

Polymerizations of methacryloxypropyl-terminated polydimethylsiloxanemacromonomer (PDMS) with acrylic acid (AA), N,N-dimethylaminoethylmethacrylate (DMAEMA) and n-butyl methacrylate (NBM).

To a mixture of 20 parts of PDMS (MW=20,000) 2-5 parts of AA, 5 parts ofDMAEMA and 70-73 parts of NBM in 200 parts of ethyl acetate was added0.5 parts of benzoyl peroxide. This solution was purged with nitrogenand sealed in a bottle under a nitrogen atmosphere. The bottle washeated in a Launder-O-Meter® at 60° C. for 36-48 hours and the polymerwas recovered by evaporation of solvent under reduced pressure.

    ______________________________________                                        Example   PDMS    DMAEMA       AA   NBM                                       ______________________________________                                        11        20      5            2    73                                        12        20      5            5    70                                        ______________________________________                                    

We claim:
 1. A hair composition comprising the following ingredients:(a)c copolymer which comprises repeating A, B, and C monomers wherein:A isat least one free radically polymerizable acrylic or methacrylic monomerpresent in 0.1-99.9% by weight of all monomer present; B is at least onehighly polar acrylic or methacrylic monomer copolymerizable with A anddifferent from A, the amount by weight of B monomer being from 0.1 to99.9% of the total weight of all monomers in said copolymer; and C is amonomer present as from 0.01 to 50% by weight of all monomer present andhaving the general formula

    X(Y).sub.n Si(R).sub.3-m Z.sub.m

wherein:X is a vinyl group copolymerizable with the A and B monomers; Yis divalent linking group; R is hydrogen, lower alkyl, aryl, or alkoxy;having a number of average molecular weight of at least about 500 and isessentially unreactive under copolymerization conditions; n is zero or1; m is an integer of from 1 to 3; and (b) a medicinally effectiveamount of a medicament or a cosmetically effective amount of aconditioner or cosmetically active ingredient;wherein (a) and (b) arepresent as a solution, dispersion, or emulsion in a liquid carryingmedium.
 2. A hair composition according to claim 1 wherein said Amonomer is a methacrylic or acrylic acid ester of an alcohol having from1 to 18 carbon atoms with the average number of carbon atoms being about4 to
 12. 3. A hair composition according to claim 1 wherein B is amonomer or multifunctional hydroxy group containing moleculesrepresented by the general formula:

    CH.sub.2 ═CR.sup.2 --CO--L--R.sup.3 --(OH).sub.d

where R² =H, methyl, ethyl, cyano or carboxymethyl, L=O, NH, d=1-3 andR³ is a hydrocarbyl radical of valence d+1 containing from 1-12 carbonatoms.
 4. A hair composition according to claim 1 wherein said X groupof acid C monomer has the general formula ##STR7## wherein R⁷ ishydrogen or a COOH group and R⁸ is hydrogen, a methyl group, or a CH₂COOH group.
 5. A hair composition according to claim 1 wherein said Zgroup of said monomer has the general formula ##STR8## wherein: R⁹ andR¹¹ are independently lower alkyl, aryl, or fluoroalkyl;R¹⁰ is alkyl,alkoxy, alkylamino, aryl, hydroxyl, or fluoroalkyl; and e is an integerfrom about 5 to about
 700. 6. A hair composition according to claim 1wherein said C monomer has a general formula selected from the groupconsisting of ##STR9## wherein R" is alkyl or hydrogen;m is 1, 2 or 3; gis zero or 1; f is an integer from 2 to 6; h is an integer from 0 to 2.7. A hair composition according to claim 1 wherein the molecular weightof said C monomer is in the range of about 500 to about 50,000.
 8. Ahair composition according to claim 1 wherein the molecular weight ofsaid C monomer is in the range of about 5,000 to about 25,000.